Silicone adhesives, articles, and methods

• US 6,703,120 B1
• Filed: 04/11/2002
• Issued: 03/09/2004
• Est. Priority Date: 05/05/1999
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Melancon, Kurt C., Ko, John H., Schulz, Anita L.
• Primary Examiner(s): Dawson, Robert
• Assistant Examiner(s): KEEHAN, CHRISTOPHER M
• Application Number:
  US10/009,928
• Time in Patent Office: 698 Days
• Field of Search: 428/355.R, 428/354, 428/447, 428/448, 428/66.3, 428/40.1, 428/351, 428/458, 525/477, 525/478, 528/15, 528/35, 435/288.1, 435/288.4, 435/305.3, 435/305.4
• US Class Current: 428/355.00R
• CPC Class Codes: B01L 2300/044 pierceable, e.g. films, membranes
• CPC Class Codes: B01L 2300/12 Specific details about materials
• CPC Class Codes: B01L 2300/16 Surface properties and coatings
• CPC Class Codes: B01L 3/50853 with covers or lids
• CPC Class Codes: C08L 2205/035 containing four or more polymers in a blend
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C09J 183/04 Polysiloxanes
• CPC Class Codes: Y10T 428/214 End closure
• CPC Class Codes: Y10T 428/2835 including moisture or waterproof component
• CPC Class Codes: Y10T 428/2848 Three or more layers
• CPC Class Codes: Y10T 428/2852 Adhesive compositions
• CPC Class Codes: Y10T 428/298 Physical dimension
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

The present invention provides silicone-based adhesives, preferably pressure sensitive adhesives, adhesive articles, and methods. Preferably, the articles are cover tapes for analytical receptacles, such as microtiter plates, microfluidic devices, and continuous multi-reservoir carriers, or other analytical receptacles or biosensors, for example. Typically, such analytical receptacles are used in bioanalytical applications and are designed for containing solids and fluids, including liquids, gases, powders, and gels, which may include biological samples or organic solvents, for example.

Claims

1. An adhesive prepared from components comprising:

(a) a polydiorganosiloxane having the general formula R¹R₂SiO(R₂SiO)_nSiR₂R¹ and a number average molecular weight of at least 20,000, wherein each R is independently a monovalent hydrocarbon group, each R¹ is independently an alkenyl group, and n is an integer;

(b) a polydiorganosiloxane having the general formula R¹R₂SiO(R₂SiO)_m(R¹RSiO)_nSiR₂R¹ and a number average molecular weight of less than 20,000, wherein each R and R¹ is independently a monovalent hydrocarbon group at least two R¹ groups are alkenyl groups, and m and n are integers the sum of which provide an alkenyl equivalent weight of about 250 to about 10,000;

(c) an organopolysiloxane MQ resin which contains (R²)₃SiO_1/2 units and SiO₂ units in a molar ratio in the range of 0.6;

1 to 1;

1, wherein each R² is independently selected from the group of alkyl groups, alkenyl groups, or hydroxyl groups, wherein at least 95 mole percent of all R² groups are methyl groups;

(d) an organohydrogenpolysiloxane free of aliphatic unsaturation having an average of at least 2 silicon-bonded hydrogen atoms in each molecule, in a quantity sufficient to provide from 1 to 40 silicon-bonded hydrogen atoms per alkenyl group in components (a) through (c); and

(e) a Group VIIB-containing catalyst in a quantity sufficient to provide 0.1 to 1,000 weight parts Group VIIIB metal for each one million weight parts of the combined quantity of components (a) through (d);

wherein when the adhesive is disposed on a propylene/ethylene copolymer backing at a coating weight of 0.8 grams/154.8 cm² and adhered to a polypropylene plate displays a 180°

peel force of at least about 5 N/dm when measured at 30.5 cm/minute and room temperature.

2. The adhesive of claim 1 wherein the organopolysiloxane MQ resin includes both nonfunctional and functional MQ resins.

3. The adhesive of claim 2 wherein the functional MQ resin includes alkenyl groups.

9. The adhesive of claim 1 which is a pressure sensitive adhesive.

10. An adhesive article comprising a substrate having disposed on at least one major surface the silicone-based adhesive of claim 1.

11. The adhesive article of claim 10 wherein the organopolysiloxane MQ resin includes both nonfunctional and functional MQ resins.

12. The adhesive article of claim 10 further comprising a release line disposed on the adhesive.

16. The adhesive article of claim 10 wherein the substrate comprises a puncturable material.

17. The adhesive article of claim 10 wherein the adhesive is a pressure sensitive adhesive.

18. An analytical receptacle comprising a surface and a cover tape adhered to the surface;

wherein the cover tape comprises a backing and the adhesive of claim 1 disposed on at least one major surface of the backing and in contact with the receptacle surface.

19. The analytical receptacle of claim 18 further comprising one or more reservoirs in the form of a well or channel.

20. The analytical receptacle of claim 18 wherein the analytical receptacle comprises a substantially continuous tape.

21. The analytical receptacle of claim 18 wherein the adhesive is a pressure sensitive adhesive.

25. The analytical receptacle of claim 18 further comprising one or more reservoirs including a liquid therein during use.

26. The analytical receptacle of claim 25 wherein the liquid comprises dimethyl sulfoxide, water, acetonitrile/water, methanol, ethanol, or mixtures thereof.

27. The analytical receptacle of claim 18 comprising a microtiter plate.

28. The analytical receptacle of claim 18 comprising a microfluidic device comprising a substrate and one or more channels therein.

29. The analytical receptacle of claim 18 comprising a substantially continuous polymeric strip comprising a plurality of reservoirs at predetermined intervals along its length.

30. The analytical receptacle of claim 29 wherein the reservoirs are uniformly spaced.

34. A method of sealing an analytical receptacle comprising applying a cover tape comprising a backing and the adhesive of claim 1 disposed on at least one major surface thereof.

4. An adhesive prepared from components comprising:

(a) a polydiorganosiloxane having the general formula R¹R₂SiO(R₂SiO)_nSiR₂R¹ and a number average molecular weight of at least 20,000, wherein each R is independently a monovalent hydrocarbon group, each R¹ is independently an alkenyl group, and n is an integer;

(b) a polydiorganosiloxane having the general formula R¹R₂SiO(R₂SiO)_m(R¹RSiO)_nSiR₂R¹ and a number average molecular weight of less than 20,000, wherein each R and R¹ is independently a monoyalent hydrocarbon group, at least two R¹ groups are alkenyl groups, and m and n are integers the sum of which provide an alkenyl equivalent weight of about 250 to about 10,000;

(c) an organopolysiloxane MQ resin which contains (R²)₃SiO_1/2 units and SiO₂ units in a molar ratio in the range of 0.6;

1 to 1;

1, wherein each R² is independently selected from the group of alkyl groups, alkenyl groups, or hydroxyl groups, wherein at least 95 mole percent of all R² groups are methyl groups;

(d) an organohydrogenpolysiloxane free of aliphatic unsaturation having an average of at least 2 silicon-bonded hydrogen atoms in each molecule, in a quantity sufficient to provide from 1 to 40 silicon-bonded hydrogen atoms per alkenyl group in component (a) through (c); and

(e) a Group VIIIB-containing catalyst in a quantity sufficient to provide 0.1 to 1,000 weight parts Group VIIIB mental for each one million weight parts of the combined quantity of components (a) through (d);

wherein when the adhesive is disposed on a fluorosilicone-coated polyethylene terephthalate release liner and a propylene/ethylene copolymer backing at a coating weight of 0.8 grams/154.8 cm² to form a laminate, and when adhered to a glass plate, displays a 180°

release force of no grater than about 20 N/dm when measured at 30.5 cm/minute and room temperature.

5. The adhesive of claim 4 which displays a release force of no greater than about 15 N/dm.

6. The adhesive of claim 5 which displays a release force of no greater than about 10 N/dm.

7. The adhesive of claim 6 which displays a release force of no greater then about 5 N/dm.

8. The adhesive of claim 4 when disposed on a propylene/ethylene copolymer backing at a coating weight of 0.8 grams/154.8 cm² and adhered to a polypropylene plate displays a 180°

peel force of at least about 5 N/dm when measured at 30.5 cm/minute and room temperature.

13. An adhesive article comprising a substrate having disposed on at least major surface the silicone-based adhesive of claim 4.

14. The adhesive article of claim 13 wherein the adhesive displays a release force of no greater than about 5 N/dm.

15. The adhesive article of claim 13 wherein the adhesive when disposed on a propylene/ethylene copolymer backing at a coating weight of 0.8 grams/154.8 cm² and adhered to a polypropylene plate displays a 180°

peel force of at least about 5 N/dm when measured at 30.5 cm/minute and room temperature.

22. An analytical receptacle comprising a surface and a cover tape adhered to the surface;

wherein the cover tape comprises a backing, and the adhesive of claim 4 disposed on at least one major surface of the backing and in contact with the receptacle surface.

23. The analytical receptacle of claim 22 wherein the adhesive display a release force of no greater than about 5 N/dm.

24. The analytical receptacle of claim 22 wherein the adhesive when disposed on a propylene/ethylene copolymer backing at a coating weight of 0.8 grams/154.8 cm² and adhered to a polypropylene plate displays a 180°

peel force of at least about 5 N/dm when measured at 30.5 cm/minute and room temperature.

38. A method of sealing an analytical receptacle comprising applying a cover tape comprising a backing and the adhesive of claim 4 disposed on at last one major surface thereof.

31. An analytical receptacle comprising a surface comprising polypropylene,polystyrene, or combination thereof, and a cover tape adhered to the surface;

wherein the cover tape comprises a backing and an adhesive disposed on at least one major surface of the backing and in contact with the receptacle surface, wherein the adhesive is prepared from components comprising;

(a) a polydiorganosiloxane having the general formula R¹R₂SiO(R₂SiO)_nSiR₂R¹ wherein each R is independently a monovalent hydrocarbon group, each R¹ is independently an alkenyl group and n is an integer;

(b) an organopolysiloxane MQ resin which contains (R²)₃SiO_1/2 units and SiO₂ units in a molar ratio in the range of 0.6;

1 to 1;

1, wherein each R² is independently selected from the group of alkyl groups, alkenyl groups, or hydroxyl groups, wherein at least 95 mole percent of all R² groups are methyl groups;

(c) an organohydrogenpolysiloxane free of aliphatic unsaturation having an average of at least 2 silicon-bonded hydrogen atoms in each molecule, in a quantity sufficient to provide from 1 to 40 silicon-bonded hydrogen atoms per alkenyl group in component (a) and component (b) if present; and

(d) a Group VIIIB-containing catalyst in a quantity sufficient to provide 0.1 to 1,000 weight parts Group VIIIB metal for each one million weight parts of the combined quantity of components (a) through (c);

wherein when the adhesive is disposed on a propylene/ethylene copolymer backing at a coating weight of 0.9 grams/154.8 cm² and adhered to a polypropylene plate displays a 180°

peel force of at least about 5 N/dm when measured at 30.5 cm/minute and room temperature.

32. An analytical receptacle comprising a surface and a cover tape adhered to the surface;

wherein the cover tape comprises a backing and an adhesive disposed on at least one major surface of the backing and in contact with the a receptacle surface, wherein the adhesive is prepared from components comprising;

(e) a polydiorganosiloxane having the general formula R¹R₂SiO(R₂SiO)_nSiR₂R¹ wherein each R is independently a monovalent hydrocarbon group, each R¹ is independently an alkenyl group and n is an integer;

(f) an organopolysiloxane MQ resin which contains (R²)₃SiO_1/2 units and SiO₂ units in a molar ratio in the range of 0.6;

1 to 1;

1, wherein each R² is independently selected from the group of alkyl groups, alkenyl groups, or hydroxyl groups, wherein at least 95 mole percent of all R² groups are methyl groups;

(g) an organohydrogenpolysiloxane free of aliphatic unsaturation having an average of at least 2 silicon-bonded hydrogen atoms in each molecule, in a quantity sufficient to provide from 1 to 40 silicon-bonded hydrogen atoms per alkenyl group in component (a) and component (b) if present; and

(h) a Group VIIIB-containing catalyst in a quantity sufficient to provide 0.1 to 1,000 weight parts Group VIIIB metal for each one million weight parts of the combined quantity of components (a) through (c);

wherein the adhesive when disposed on a fluorosilicone-coated polyethylene terephthalate release liner and a propylene/ethylene copolymer baking at a coating weight of 0.8 grams/154.8 cm² to form a laminate, and when adhered to a glass plant, displays a 180°

release force of no greater than about 20 N/dm when measured at 30.5 cm/minute and room temperature.

33. A method of making an adhesive comprising:

preparing a composition comprising;

(a) a polydiorganosiloxane having the general formula R¹R₂SiO(R₂SiO)_nSiR₂R¹ and a number average molecular weight of at last 20,000, wherein each R is independently a monovalent hydrocarbon group, each R¹ is independently an alkenyl group, and n is an integer;

(b) a polydiorganosiloxane having the general formula R¹R₂SiO(R₂SiO)_m(R¹R₂SiO)_nSiR₂R¹ and a number average molecular weight of less than 20,000, wherein each R and R¹ is independently a monovalern hydrocarbon group, at least two R¹ groups are alkenyl groups, and m and n are integers the sum of which provide an alkenyl equivalent weight of about 250 to about 10,000;

(c) an organopolysiloxane MQ resin which contains (R²)₃SiO_1/2 units and SiO₂ units in a molar ratio in the range of 0.6;

1 to 1;

1, wherein each R² is independently selected from the group of alkyl groups, alkenyl groups, or hydroxyl groups, wherein at least 95 mole percent of all R² groups are methyl groups;

(d) an organohydrogenpolysiloxane free of aliphatic unsaturation having an average of at least 2 silicon-bonded hydrogen atoms in each molecule, in a quantity sufficient to provide from 1 to 40 silicon-bonded hydrogen atoms per alkenyl group in components (a) through (c); and

(e) a Group VIIIB-containing catalyst in a quantity sufficient to provide 0.1 to 1,000 weight parts Group VIIIB metal for each one million weight parts of the combined quantity of components (a) through (d); and

thermally curing the composition;

wherein when the adhesive is disposed on a propylene/ethylene copolymer backing at a coating weight of 0.8 grams/154.8 cm² and adhered to a polypropylene plate displays a 180°

peel force of at least about 5 N/dm when measured at 30.5 cm/minute and room temperature.

35. An analytical receptacle comprising a surface comprising polypropylene, polystyrene, or combination thereof, and a cover tape adhered to the surface, wherein the cover tape comprises a backing and an adhesive disposed on at leat one major surface of the backing and in contact with the receptacle surface, wherein the adhesive is prepared from components comprising:

(i) a polydiorganosiloxane having the general formula R¹R²SiO(R₂SiO)_nSiR₂R¹ wherein each R is independently a monovalent hydrocarbon group, each R¹ is independently an alkenyl group and n is an integer,

(j) an organopolysiloxane MQ resin which contains (R²)₃SiO_1/2 units and SiO₂ units in a molar ratio in the range of 0.6;

1 to 1;

1, wherein each R² is independently selected from the group of alkyl groups, alkenyl groups, or hydroxyl groups, wherein at least 95 mole percent of all R² groups are methyl groups;

(k) an organohydrogenpolysiloxane free of aliphatic unsaturation having an average of at least 2 silicon-bonded hydrogen atoms in each molecule, in a quantity sufficient to provide from 1 to 40 silicon-bonded hydrogen atoms per alkenyl group in component (a) and component (b) if present; and

(l) a Group VIIIB-containing catalyst in a quantity sufficient to provide 0.1 to 1,000 weight parts Group VIIIB metal for each one million weight park of the combined quantity of components (a) through (c);

wherein the adhesive when disposed on a fluorosilicone-coated polyethylene terephthalate release liner and a propylene/ethylene copolymer backing at a coating weight of 0.8 grams/154.8 cm² to form a laminate, and when adhered to a glass plate, displays a 180°

release force of no greater than about 20 N/dm when measured at 30.5 cm/minute and room temperature.

36. An analytical receptacle comprising a surface and a cover tape adhered to the surface;

wherein the cover tape comprises a backing and an adhesive disposed on at least one major surface of the backing and in contact with the receptacle surface, wherein the adhesive is prepared from components comprising;

(m) a polydiorganosiloxane having the general formula R¹R₂SiO(R₂SiO)_nSiR₂R¹ wherein each R is independently a monovalent hydrocarbon group, each R¹ is independently an alkenyl group and n is an integer,

(n) an organopolysiloxane MQ resin which contains (R²)₃SiO_1/2 units and SiO₂ units in a molar ratio in the range of 0.6;

1 to 1;

1, wherein each R² is independently selected from the group of alkyl groups, alkenyl groups, or hydroxyl groups, wherein at least 95 mole percent of all R² groups are methyl groups;

(o) an organohydrogenpolysiloxane free of aliphatic unsaturation having an average of at least 2 silicon-bonded hydrogen atoms in each molecule, in a quantity sufficient to provide from 1 to 40 silicon-bonded hydrogen atoms per alkenyl group in component (a) and component (b) if present; and

(p) a Group VIIIB-containing catalyst in quantity sufficient to provide 0.1 to 1,000 weight parts Group VIIIB metal for each one million weight parts of the combined quantity of components (a) though (c);

wherein when the adhesive is disposed on a propylene/ethylene copolymer backing at a coating weight of 0.8 grams/154.8 cm² and adhered to a polypropylene plate display a 180°

peel fore of at least about 5 N/dm when measured at 30.5 cm/minute and room temperature.

37. A method of making an adhesive comprising:

preparing a composition comprising;

(f) a polydiorganosiloxane having the general formula R¹R₂SiO(R₂SiO)_mSiR₂R¹ and a number average molecular weight of at least 20,000, wherein each R is independently a monovalent hydrocarbon group, each R¹ is independently an alkenyl group, and n is an integer,

(g) a polydiorganosiloxane having the general formula R¹R₂SiO(R₂SiO)_m(R¹R₂SiO)_nSiR₂R¹ and a number average molecular weight of less than 20,000, wherein each R and R¹ is independently a monovalent hydrocarbon group, at least two R¹ groups are alkenyl groups, and m and n are integers the sum of which provide an alkenyl equivalent weight of about 250 to about 10,000;

(h) an organopolysiloxane MQ resin which contains (R²)₃SiO_1/2 units and SiO₂ units in a molar ratio in the range of 0.6;

1 to 1;

1, wherein each R² is independently selected from the group of alkyl groups, alkenyl groups, or hydroxyl groups, wherein at least 95 mole percent of all R² groups are methyl groups;

(i) an organohydrogenpolysiloxane free of aliphatic unsaturation having an average of at least 2 silicon-bonded hydrogen atoms in each molecule, in a quantity sufficient to provide from 1 to 40 silicon-bonded hydrogen atoms per alkenyl group in components (a) through (c); and

(j) a Group VIIIB-containing catalyst in a quantity sufficient to provide 0.1 to 1,000 weight parts Group VIIIB metal for each one million weight parts of the combined quantity of components (a) through (d); and

thermally curing the composition;

wherein the adhesive when disposed on a fluorosilicone-coated polyethylene terephthalate release liner and a propylene/ethylene copolymer backing at a coating weight of 0.8 grams/154.8 cm² to form a laminate, and when adhered to a glass plate, displays a 180°

release force of no greater than about 20 N/dm when measured at 30.5 cm/minute and room temperature.